Oil-soluble lubricant bi-functional additives from mannich condensation products of oxidized olefin copolymers, amines and aldehydes

ABSTRACT

Bi-functional lubricant additives exhibiting dispersant and V.I. improving properties are obtained by the Mannich Condensation of an oxidized long-chain high molecular weight amorphous copolymer of essentially ethylene and propylene having a number average molecular weight of at least about 10,000 and at least 140 pendant methyl groups per 1,000 chain carbon atoms, with a formaldehyde yielding reactant and a primary or secondary amine or polyamine, said reactants being employed in the molar ratio of from about 1:2:2 to about 1:20:20, respectively.

Uited States atent 91 Culbertson et a1.

[11] 3,872,019 Mar. 18, 1975 1 OIL-SOLUBLE LUBRICANT Bl-FUNCTIONALADDITIVES FROM MANNICH CONDENSATION PRODUCTS OF OXIDIZED OLEFINCOPOLYMERS, AMINES AND ALDEHYDES [75] Inventors: George S. Culbertson,Downers Grove; Gary R. Chipman, Naperville; Robert E. Karll, Batavia,

all of Ill.

[73] Assignee: Standard Oil Company, Chicago, Ill.

[22] Filed: Aug. 8, 1972 [21] Appl. No.: 278,719

[52] US. Cl....llI....I..f..f7fl5i. A, 252/515 R.

260/33.6 UA, 260/72 R, 260/854 [51] Int. Cl C08g 9/04, C08g 37/32, ClOm1/32 [58] Field ofs'ar'tii...26o/72 R; 252/515 R, 51.5 A, 252/854 [56] 9References Cited UNITED STATES PATENTS 3,316,177 4/1967 Dorer 252/51512/1970 Culbertson et a1. 260/72 3,647,692 3/1972 Lee 252/515 PrimaryE.raminerHoward E. Schain Attorney, Agent, or Firm-Fred R. Ahlers;Arthur G. Gilkes; William T. McClain [57] ABSTRACT lecular weight of atleast about 10,000 and at least 140 pendant methyl groups per 1,000chain carbon atoms, with a formaldehyde yielding reactant and a primaryor secondary amine or polyamine, said reactants being employed in themolar ratio of from about 1:222 to about 1:20:20, respectively.

13 Claims, N0 Drawings BACKGROUND OF THE INVENTION Lubricantdeterioration in high speed engines causes the formation of lacquer,sludge and carbon deposits on the interior surfaces of the engines whichaccelerates wear and reduces engine efficiency. To reduce the tendencyfor such deleterious products to deposit on the surfaces of the engineit is known to incorporate in the lubricating oil additives havingdispersancy and/or detergency properties.

The continuing search for and the necessity of having available ashlessdispersants and/or detergents additives for motor oils is well known.Since the development of the positive crankcase ventilation system (PCV)there is a greater demand than ever for improved additives of suchtypes.

It is also well known that lubricating oils have a tendency to becomethin at elevated temperatures while becoming thick at low temperatures,and thus it is generally necessary to add additives to such lubricantswhich improve their viscosity-temperature relationships. For example, inthe case of a crankcase lubricating oil in a cold engine, it isdesirable that the oil not become so thick that it is difficult to startthe engine; while, when the engine is hot it is necessary that the oilremain sufficiently viscous that an oil film is maintained between themoving parts.

Various products have been developed for the purpose of providing thedispersant and/or detergent function. Neutral and overbasedmetallo-organic compounds, such as the alkaline earth salts of sulfonicacids, and hydrocarbon-P 5 reaction products were among the firstaddition agents used for this purpose. Their in-service drawbacksinclude the formation of undesirable metal-ash thermal decompositionproducts. Other proposed additives were amine salts, amides, imides andamidines of polybutenyl-substituted polycarboxylic acids. Still otherproposed additives were combinations of alkaline earth sulfonates andMannich condensation products of low molecular weight alkyl-substitutedhydroxyaromatic compounds, amines having at least one replaceablehydrogen on a nitrogen, and aldehydes; alkaline earth salts of suchMannich condensation products have also been suggested.

Mannich condensation products derived from alkylsubstitutedhydroxyaromatic compounds having a relatively low molecular weight alkylsubstituent, i.e., 2 to carbon atoms in the alkyl substituent aredescribed in U.S. Pat. Nos. 2,403,453;.2,353,49l; 2,363,134; 2,459,112;2,984,550 and 3,036,003. U.S. Pat. No. 3,368,972 describes as dispersantand/or detergent addition agents for lubricating oils high molecularweight Mannich condensation products from high molecular weightalkyl-substituted hydroxyaromatic compounds, in which thealkyl-substituent has a molecular weight in the range of 600-3,000; anamine and an aldehyde. However, such condensation products do notexhibit bi-functional dispersancy and V.l. improving properties.

Culbertson et a1. U.S. Pat. No. 3.544,5 20 issued Dec. 1, 1970,discloses and claims as ashless dispersants the products prepared bysubjecting an olefin polymer hav- LII ing a molecular weight of aboutZOO-2,000; such as a polybutene or polypropylene to oxidation in thepresence of a catalyst such as manganous carbonate, and the oxidizedpolymer then condensed with formaldehyde and a polyalkylene polyamine.Such condensation products while effective as ashless dispersants, donot impart V.I. improving properties to lubricating oils.

Additives, imparting sludge inhibiting and detergent properties tolubricating oils, prepared by reacting,oxidized degraded interpolymersof propylene and ethylene having a molecular weight of at least about1,000. with maleic anhydride, and neutralizing the acidic intermediatewith an alkylene polyamine, is described in U.S. Pat. No. 3,316,177.

We have discovered a product prepared as hereinafter described which isuseful as a lubricant additive possessing both dispersant and V.I.improving properties, which bifunctional properties are not exhibited bythe additives described in the above prior art patents.

SUMMARY OF THE INVENTION In accordance with the present invention, thebifunctional additive is prepared by reacting simultaneously, at atemperature of about 250-350F., an oxidized copolymer (as hereinafterdefined) of ethylene and propylene with a formaldehyde-yieldingreactant, and an aliphatic amine or polyamine, and recovering theresultant reaction product; said reactants being employed in the molarratio of from 1:212 to about 1:20:20.

In the preparation of the additive of this invention it is desirable toconduct the Mannich condensation in the presence of a non-reactiveorganic solvent or diluent, such as, for example, an aromatichydrocarbon solvent e.g. benzene, xylene, toluene etc., or an aliphatichydrocarbon solvent, such as hexane, for example. Particularly suitableas a solventor diluent is a low viscosity hydrocarbon oil, such as asolvent-extracted SAE 5W mineral oil. The use ofa solvent or diluent isparticularly advantageous to facilitate the mixing of the reactants, andthe control of the reaction temperatures.

THE COPOLYMER' The term copolymer as used herein and in the appendedclaims, refers to amorphous copolymers derived from essentially ethyleneand propylene; however, such copolymers may contain minor amounts, i.e.,up to 10 percent, based on the molar amounts of the monomeric ethyleneand propylene units in the copolymer, of polymerized units derived fromother olefin monomers. Such other olefin monomers include olefins of thegeneral formula RCH=CH in which R is an aliphatic or cycloaliphaticradical of from 2 to about 20 carbon atoms, for example,butenel,hexene-l, 4-methy1-l-pentene, decene-l, vinylidene norbornene,S-methylene-Z-norborene, etc. Other olefin monomers having a pluralityof double bonds may be used, in particular diolefins containing fromabout 4 to about 25 carbon atoms, e.g., 1,4-butadiene, 1,3- hexadiene,l,4-pentadiene, 2-methyl-1,5-hexadiene, 1,7-octadiene etc.

Suitable ethylene-propylene copolymers contain from about 30 to about65, preferably from about 35 to about 45 mole percent propylene, have anumber average molecular weight of at least about 20,000, i.e., fromabout 20,000 to about 200,000 or more, and preferably from about 25,000to about 40,000, and contain at least 150 pendant methyl groups per1,000 chain carbon atoms.

A particularly suitable ethylene-propylene copolymer is one having thefollowing characteristics:

Number Average Molecular Weight Percent (Molar) Propylene MonomerPendant Methyl Groups per L000 Chain Carbon Atoms Inherent ViscosityGardner Viscosity Mooney Viscosity (A) O.I gram copolymer in I ccdccnlin .il I3SC. (B) 3.0% copolymer in toluene at 25C. (C) ASTM D4646U-V (B) -35 (C) OXIDATION OF THE COPOLYMER The oxidation can beaccomplished by contacting the copolymer under suitable conditions oftemperature and at atmospheric or elevated pressures, with an oxidizingagent such as air or free oxygen, or any oxygencontaining materialcapable of releasing oxygen under the oxidation conditions. If desired,the oxidation can be conducted in the presence of known oxidationcatalysts, such as platinum or a platinum group metal, and compoundscontaining metals such as copper, iron, cobalt, cadmium,manganese,vanadium etc. The oxidation can be carried out by methodsdescribed in US. Pat. Nos. 2,982,728; 3,316,177; 3,153,025; 3,365,499;and 3,544,520.

Generally, the oxidation can be carried out over a wide temperaturerange, depending upon the oxidizing agent used; for example, with anactive oxidizing agent,

e.g., S0 temperatures in the range of -F. to 400F. have been used, whilewith less active oxidizing agents, e.g., air, temperatures in the rangeof l00800F. have been used. Further, depending upon the rate desired,the oxidation can be conducted at sub-atmospheric, atmospheric orsuper-atmospheric pressures, and in the presence or absence of oxidationcatalysts. The conditions of temperature, pressure, oxygen content ofthe oxidizing agent, the rate of introducing the oxidizing agent, thecatalyst employed, if any, etc., are correlated and controlled, by thoseskilled in the art, so as to obtain the desired optimum results.

The following will illustrate one method of oxidizing the copolymer; toa copolymer of ethylene and propylene (1 part), having a number averagemolecular weight of about 28,000, was added a solvent-extracted SAE 5Wmineral oil(9 parts) in an open reaction vessel, and the mixture slowlystirred and heated at a temperature of 360F., under an inert gasatmosphere, until solution of the rubber-like polymer in the solvent waseffected. Maintaining the 360F. temperature, the mixture was rapidlyagitated in an atmosphere composed of 50 percent air and 50 percentnitrogen, to promote the oxidation of the copolymer. A 50:50air-nitrogen ratio was used to preclude the possibility of an explosivemixture being formed. Reaction in the described manner was continued for2.5-4.0 hours. About 550 oxygen atoms per molecule of the copolymer wereintroduced under such oxidation conditions.

THE AMINE REACTANT The amine reactant used in the preparation of theproducts of the present invention are primary or secondary aliphaticamines and diamines of the general formula H N(CH ),,NH wherein y is aninteger 3 to 10, said amines and diamines containing up to about 10carbon atoms in the alkyl group, and polyalkylcne polyamines of thegeneral formula wherein A is a divalent alkylene radical of about 2 toabout 6 carbon atoms, and x is an integer from I to about 10.Illustrative of suitable amines are: methylamine, dibutylamine,cyclohexylamine, propylamine, decylamine, ethylene diamine, trimethylenediamine, tetramethylene diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, tripropylenetetramine, tetrapropylene pentamine, and other polyalkylene polyaminesin which the alkylene groups contain suitably up to about 10 carbonatoms.

THE ALDEHYDE REACTANT Illustrative of aldehydes suitable for use inaccordance with the present invention are aliphatic aldehydes such as,for example, formaldehyde, acetaldehyde, b-hydroxybutyraldehyde. Weprefer to use formaldehyde or a formaldehyde-yielding compound such asparaformaldehyde and formalin.

The chemical composition of the reaction product of this inventioncannot be characterized with preciseness by chemical structural formula.While it is believed that the oxidation of the copolymer producespredominately ketones, it is known that minor amounts of aldehydes,acids and perhaps esters may also be present. In view of the complexnature of the oxidized reaction product, the precise composition of suchproduct cannot be defined by its chemical structure, but rather must bedefined by its method of preparation.

The herein described reaction products of the present invention areeffective bifunctional dispersant and V.I. improving additives inoleaginous lubricant compositions when used in amounts of from about 0.1to about 10 percent..Suitable lubricating base oils are mineral oils,i.e., petroleum oils, synthetic lubricating oils, such as those obtainedby the polymerization of hydrocarbons, and other well-known syntheticlubricating oils, and lubricating oils of animal or vegetable orgin.Concentrates of a suitable oil base containing more than 10, i.e., fromabout 10 percent to about percent or more, of the additive of thepresent invention, alone or in combination with other well-knownadditives, can be used for blending with lubricating oils in proportionsdesired for particular conditions or use to give a finished productcontaining from about 0.1 to about 10 percent of bifunctional additiveof this invention.

PREFERRED EMBODIMENTS OF THE INVENTION The following examples areillustrative of preferred embodiments of the present invention.

EXAMPLE 1 Part A Preparation of the Copolymer An amorphousethylene-propylene copolymer was prepared by solution polymerizationusing a Ziegler- Natta type catalyst, vanadium oxytrichloride solutionin combination with an ethylaluminum sesquichloride solution. Dryn-heptane (1200 ml.) was saturated at 86F. and 30 p.s.i.g. with a gasmixture consisting of 50 mole percent ethylene, 35 mole percentpropylene and 15 mole percent hydrogen. The gas mixture was introducedat the rate of 100 liters per hour, circulated through the heptane, andthen passed out of the system. When saturation was complete, theaddition of the catalyst components, in heptane solution was started.The vanadium oxytrichloride solution (0.370 percent by weight) wasintroduced into the olefin mixture at the rate of 13 ml/hr., and theethylaluminum sesquichloride solution (0.459 percent-wt.) at the rate of60 ml/hr; the molar ratio of Al/V was 8.06. When polymerization beganthe inflow of the propylene and of the ethylene was adjusted tocompensate for the greater reactivity of the latter. The average ratioof propylene- /ethylene by weight was 2.3 (as determined by periodic gaschromatographic analyses). After 1.25 hours polymerization was stoppedby displacing the gas mixture with nitrogen and stopping the catalystaddition. The reaction mixture was then washed twice with methanol todeactivate and remove the catalyst. The yield based on the amount ofvanadium catalyst used was 1680 grams of polymer per gram of VOC1 Therecovered opolymer had a number average molecular weight (M,,) of 28,000(determined by vapor pressure osmometry); 159 pendant methyl groups per1000 chain carbon atoms (determined by infrared spectroscopy), and aninherent viscosity of 2.28 dl/g. (measured in decalin at 135C. and 0.1g./100 ml.).

Part B Oxidation of the Copolymer A solution of 70 grams ofthecopolymer, obtained in Part A, above, in 1000 grams of heptane washeated to 250F. while blowing with nitrogen to remove the heptane. 280grams ofa SAE 5W mineral oil was gradually added as the heptane wasremoved, and the viscous oil copolymer mixture brought to 430F. withvigorous stirring. Blowing with nitrogen was discontinued at this point,to allow atmospheric oxygen to diffuse into the reaction vessel. After0.5 hour, thermal and oxidative degradations reduced the viscosity ofthe mixture such that vigorous stirring could be maintained at theoptimum oxidation temperature of 310F. Heating with stirring wascontinued at such temperature for a total of 2.5 hours. Conversion, asmeasured by silica gel chromatography, was 100 percent.

Part C Condensation of Oxidized Copolymer with Aldehyde and amine To 665grams of the oil solution of the oxidized copolymer from Part B, above,(20.0 percent active oxidized copolymer) were added 900 grams ofbenzene, and the solution heated to 120F. Solid paraformaldehydc (0.69grams; 0.52 percent by weight on oxidized copolymer) was then added, andthe mixture heated to a temperature of 140F. over a 0.5 hour period.Hexamethylene diamine (2.66 grams; 2.0 percent by weight on the oxidizedcopolymer) was then added I and the solution refluxed vigorously forthree hours at 176F.

The resultant condensation product was then heated at 300F., withnitrogen blowing, for one hour to remove the benzene solvent. Theactivity of the solventfree product was adjusted to 13 percent by theaddition of the SAE 5W oil.

The recovered condensation product was crystal clear, had a color of6.70 (ASTM color scale), and contained 0.06 percent nitrogen and 0.1percent oxygen.

EXAMPLE 2 Part A Oxidation of the Copolymer A solution of grams of thecopolymer, obtained in Part A of Example 1, above, in 1,000 grams ofheptane was heated to 250F., while blowing with nitrogen to remove theheptane. 630 grams of a solvent-extracted SAE 5W mineral oil wasgradually added as the heptane was removed, and the viscous oil-polymermixture heated to a temperature of 360F. with vigorous stirring andnitrogen blowing. These conditions were maintained for 0.5 hour toremove the last traces of the heptane solvent. Blowing with purenitrogen was discontinued at this point, and a gas atmosphere composedof 50 percent air and 50 percent nitrogen was introduced. Heating at360F. with vigorous stirring was continued for a total of three hours.Conversion, as measured by silica gel chromatography, was percent.Carbonyl content of the oxidized product, as measured by the infraredabsorbance band at 5.8 microns, was 7.5 absorbance units, (0.002 inchcell thickness). Oxygen analysis of the product gave 0.89 percentoxygen.

Part B -Condensati0n Product of Oxidized Copolymer with Aldehyde andAmine Two hundred grams of the oxidized copolymer, obtained in Part A,above, (10 percent active oxidized c0- polymer in SAE 5W mineral oildiluent), was heated to 320F. under a nitrogen blanket. Solidparaformaldehyde (0.38 grams; 1.9 wt. percent on the oxidized copolymer)and molten anhydrous hexamethylene diamine (1.5 grams; 7.5 wt. percenton the oxidized copolymer) were added simultaneously to the stirredreaction mixture maintained at a temperature of 320F. under a nitrogenblanket. Stirring and heating at said temperature were continued for twohours, during which time the Mannich condensation was effected with theevolution of water.

At the end of the two hour reaction period, the resultant condensationproduct was blown vigorously with nitrogen for 0.5 hour to remove anyremaining volatile by-products. The reaction product was filtered,yielding a crystal-clear product having the following inspections:

Percent Active Condensation Product 10.0 Percent nitrogen 0.185 Percentoxygen 0.45 Color (ASTM) 7.0 Viscosity (SSU at 210F.) 3200 EXAMPLE 3Part A Oxidation of the Copolymer A solution of grams of the copolymerobtained in Part A of Example 1, above, in 1745 grams of heptane washeated to 250F. under a stream of nitrogen to remove the heptane. Asolvent-extracted SAE W mineraloil (770 grams) was gradually added asthe heptane was being removed. After complete removal of the heptane byheating to 350F. under a stream of nitrogen, 885 grams of anoil-copolymer solution, containing 13 percent copolymer, was obtained.

Oxidation of the copolymer was effected by heating the above mixture to400F., and removing the nitrogen blanket so as to diffuse air into thereaction vessel. Stirring, at this point, was increased to effectsufficient splashing of the viscous liquid to insure intimate airliquidcontact. After 0.5 hour of reaction in this manner, oxidation of thecopolymer and attendant degradation had begun to take place, resultingin a viscosity decrease in the reaction medium. Agitation and reactiontemperature were gradually decreased while maintaining the desiredgas-liquid contact, until a temperature of 310F. was reached. Thisreaction temperature maintains a desired balance between a convenientoxidation rate, and undesirable excessive polymer degradation. After atotal reaction time of 2.5 hours, Silica Gel Chromatography indicated arecovered product containing 17 percent active oxidized products,corresponding to theoretical conversion of the copolymer to oxygenatedspecies (allowing for the typical 5-6 percent oxidation of the diluentoil).

Part B Condensation Product of the Oxidized Copolymer with Aldehyde andAmine To 885 grams of the oxidized copolymer product, obtained in PartA, above, were added 900 grams benzene, and the temperature of thesolution brought to 120F. under a nitrogen blanket, the nitrogen beingintroduced at the rate of 1.0 CFH. Powdered, anhydrous paraformaldehyde(0.62 grams, 0.0207 mole) was added in one lot, and the temperatureincreased to 140F. over a 0.5 hour period. Then molten anhydroushexamethylene diamine (2.4 grams, 0.02107 mole) was added in one lot,and the resultant mixture rapidly brought to the reflux temperature ofbenzene (176F.). Molar ratios of the reactants were 1:4:4, respectively.

Maintaining a nitrogen blanket, benzene and water (formed as aby-product in the condensation reaction) were distilled from thereaction mass. After one hour, at a moderate distillation rate, thedistillate in the receiver was clear, indicating the'absence of residualwater; at this point the Mannich condensation was considered to becompleted. The residual benzene was removed by increasing thetemperature to 320F., and introducing nitrogen, at the rate of 6 CFH,into the reaction vessel. Heating and nitrogen blowing were continuedfor one hour'longer to remove the last traces of volatile impurities. Ayield of 99.4 percent (880 grams) of a haze-free Mannich Condensationproduct having the following inspection was obtained:

0.058% (found) 0.063% (calculated) 2100 Activity Nitrogen Viscosity (SSUat 210F.)

EXAMPLE 4 Part B of Example 3, above. However, in this example the molarratios of oxidized copolymer, paraformaldehyde, and hexamethylenediamine employed were l:8.6:8.6, respectively, on the basis, as inExample 3, above, of the oxidized copolymer having a number averagemolecular weight of 22,200. Reaction conditions and procedures foreffecting the Mannich condensation were the same as those used in Part Bof Example 3, above. A yield of 99.5 percent of a clear MannichCondensation product having the following product inspection wasobtained:

Activity 8.0% Nitrogen 0.084% (found) 0.086% (Calculated) Viscosity (SSUat 210F.) 1125 EXAMPLE 4 A copolymer of 55 mole percent ethylene, 35mole percent propylene and 10 mole percent l-decene was prepared as inPart A of Example 1, above, and then oxidized as described in Part B ofsaid Example 1. The oxidized copolymer was then reacted withparaformaldehyde and hexamethylene diamine under Mannich Condensationconditions, as described in Part C of Example 1, above; said reactantsbeing used in the molar ratios of 114:4, respectively. The recoveredMannich Condensation product had an activity of 13 percent and contained0.06 percent nitrogen.

The V.1. imparting property of the herein described Mannich Condensationproducts of the present invention is demonstrated by the data in thefollowing TABLE 1, in which the following oil samples were employed:

Sample A Neutral Base Oil Sample Sample A plus 1.1% neat (i.e.,undiluted) Mannich B Condensation product Example 1, Part C.

Sample A plus 1.5% neat Oxidized Polyisobutylene (number averagemolecular weight 1500), Mannich Condensation product.

Sample A plus 1.5% neat Oxidized Ethylene-Propylene Copolymer (numberaverage molecular weight 2000), Mannich Condensation product.

Sample Sample The above data demonstrate that the Mannich Condensationproducts of the present invention are highly efficient in imparting thedesired V.I. property to a low V.1. base oil stock.

The effectiveness of the additives of the present invention isdemonstrated by the so-called Spot Dispersancy Test. In this test, ameasured amount of the additive to be tested is mixed with a measuredvolume of crankcase lubricant oil formulation which has been used in aFord Sequence V C Engine Test for 192 hours (twice the time of thestandard test time). This composition is heated and stirred at about300F. for about 16 hours, and an aliquot is transferred to blottingpaper. A control is made at the same time by stirring and heat- SampleA:

ing at 300F. for 16 hours a second oil from the 192 hour Ford Sequence VC Engine Test, and depositing an aliquot on blotting paper. At the sametime, a readily available commercial ashless dispersant is mixed in thesame manner as above, for comparison purposes. The deposits on theblotting paper are measured to obtain the average diameter of the outeroil ring (Do), and the average diameter of the inner sludge ring (Da).The ratio of Da/Do is an indication of the detergent-dispersant propertyof the addition agent.

The data in TABLE 11 below compare the dispersancy properties of theadditive of the present invention with a commercial dispersant additive.The following samples were employed in this test:

Sample A Control Oil no dispersent Sample B Control Oil plus 1.0%Mannich Condensation product Example 3, Part B, supra. Sample C ControlOil plus 1.0% commercial dispersant-Vl additive.

TABLE II SAMPLE PERCENT DISPERSANCY A 45 B 93 C 66 Solvent-extracted SAEOil 49.8% (vol.) Solvenbextracted SAE Oil 36.8% do. Zinc dialkyldithiophosphate 1.2% do. High-base Magnesium sulfonate 1.2% do. MannichProduct. Example 3. Part B l 1.0% do.

(13% active; 1.4% [vol.] active ingredient) Sample B:

Solvent-extracted SAE 5 Oil 25.1% (vol.) Solventextracted SAE 10 Oil60.0% do. Zinc dialkyl dithiophosphate 1.2% do. High-base Magnesiumsulfonate 1.2% do. Pour point depressant 0.5% do. Mannich Product. blandof Example 3. 12.0% do. Part B and Example 4 (10% active; 1.2% [vol.]active ingredient) Sample C:

Solventextracted SAE 5 Oil 30.0% (vol.) Solvent-extracted SAE 10 Oil56.93% do. Zinc dialkyl dithiophosphate 1.1% do. High-base Magnesiumsulfonate 2.0% do. Commercial Vl lmprover 5.2% do. Silicone Anti-foamAgent 500 ppm Commercial Ashless Dispersant 4.77% do.

(42% active: 2.0% [\ol.] active ingredient) The data obtained in thesetests are given in TABLE 111, below:

TABLE III ENGINE RATINGS SAMPLE Sludge Varnish Piston Varnish A 8.4 8.57.3 B 9.5 8.6 7.5 C 9.0 8.5 8.2

The data presented in TABLES I, 11 and 111, above, demonstrate that theMannich Condensation products prepared in accordance with the presentinvention exhibit a unique combination of high level dispersancy andexcellent Vl properties.

Percentages given herein and in the appended claims are weightpercentages unless otherwise stated.

Although the present invention has been described with reference tocertain specific preferred embodiments thereof, the invention is notlimited thereto, but includes within its scope such modifications andvariations as come within the scope and spirit of the appended claims.

We claim:

1. The oil-soluble condensation product prepared by the processcomprising, reacting simultaneously at a temperature of from about 250F.to about 350F. (1) an oxidized high molecular weight amorphous copolymerof essentially ethylene and propylene, said copolymer having a numberaverage molecular weight of at least about 10,000 and at least pendantmethyl groups per 1,000 chain carbon atoms, (2) a formaldehyde-yieldingreactant and (3) a primary or secondary aliphatic amine selected fromthe group consisting of an alkyl amine having from about 2 to about 12carbon atoms, an aliphatic diamine of the general formula H N(CH ),,NHwherein y is an integer of from about 3 to about 10, and a polyalkylenepolyamine ofthe general formula wherein A is a divalent alkylene radicalof from about 2 to 6 carbon atoms, and x is an integer of from 1 toabout 10, wherein said reactants are used in the respective reactantmolar ratio of from about 112:2 to about 1:20:20.

2. The oil-soluble condensation. product of claim 1, wherein saidcopolymer comprises essentially ethylene and from about 30 to about 65mole percent propylene.

3. The oil-soluble condensation product of claim 1, wherein saidcopolymer comprises essentially ethylene, from about 30 to about 65 molepercent propylene, and up to about 20 mole percent of a third olefinicmonomer selected from the group having the general formula RCHH whereinR is an aliphatic or cycloaliphatic radical of from 2 to about 20 carbonatoms, and diolefinic monomers having from about 4 to about 25 carbonatoms.

4. The oil-soluble condensation product of claim 3, in which the thirdolefinic monomer is l-decene.

5. The oil-soluble condensation product of claim 1, in which theformaldehyde-yielding reactant is paraformaldehyde, and the aliphaticdiamine is hexamethylene diamine.

6. The oil-soluble condensation product of claim 1, in which theformaldehyde-yielding reactant is paraformaldehyde, and the polyalkylenepolyamine is tetraethylene pentamine.

7. The oil-soluble condensation product of claim 1,

in which the copolymer comprises essentially and about 38-42 molepercent propylene, said copolymer having a number average molecularweight of from about 25,000 to about 35,000, and from about 160 to about170 pendant methyl groups per 1,000 chain carbon atoms, saidformaldehyde-yielding reactant is paraformaldehyde, and said aliphaticdiamine'is hexamethylene diamine, said reactants being employed in themolar ratio of about l:l4.5:l4.5, respectively.

8. A lubricant composition comprising a major proportion of a normallyliquid oleaginous lubricant, and from about 0.1 to about percent of theoil-soluble condensation product defined in claim 1.

9. A lubricant composition comprising a major proportion of a normallyliquid oleaginous lubricant, and from about 0.1 to about 10 percent ofthe oil-soluble condensation product defined in claim 2.

10. A lubricant composition comprising, a major proportion of a normallyliquid oleaginous lubricant, and from about 0.1 to about 10 percent ofthe oil-soluble condensation product defined in claim 3.

11. A lubricant composition comprising, a major proportion of a normallyliquid oleaginous lubricant, and from about 0.1 to about 10 percent ofthe oil-soluble condensation defined in claim 4.

12. A lubricant composition comprising, a major proportion of a normallyliquid oleaginous lubricant, and from about 0.1 to about 10 percent ofthe oil-soluble condensation product defined in claim 6.

13. An addition agent concentrate for lubricating oils, comprising alubricating oil containing from about 10 to about percent of theoil-soluble condensation product defined in claim 1.

UNITED STATES PATENT OFFICE r CERTIFICATE OF PATENT NO. 3,872,019

DATED I :March 18, 1975 INVENTOR(S) 1 George S. Culbertson, Gary R.Chipman, and Robert E. Karll It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. Line r 55 "10," should be 10%, 5 5 "oil" should be oil- T 380.02107" should be 0.0207 7 6 "ethylenepropylene" should beethylene-propylene 9 55 "bland" should be "blend" 11 Following"essentially" insert ethylene Signed and sealed this 24th day of June1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officerand Trademarks

1. THE OIL-SOLUBLE CONDENSATION PRODUCT PREPARED BY THE PROCESSCOMPRISING, REACTING SIMULTANEOUSLY AT A TEMPERATURE OF FROM ABOUT250*F. TO ABOUT 350*F. (1) AN OXIDIZED HIGH MOLECULAR WEIGHT AMORPHOUSCOPOLYMER OF ESSENTIALLY ETHYLENE AND PRPROPYLENE, SAID COPOLYMER HAVINGA NUMBER AVERAGE MOLECULAR WEIGHT OF AT LEAST ABOUT 10,000 AND AT LEAST140 PENDANT METHYL GROUPS PER 1,000 CHAIN CARBON ATOMS, (2) AFORMALDEHYDE-YIELDING REACTANT AND (3) A PRIMARY OR SECONDARY ALIPHATICAMINE SELECTED FRM THE GROUP CONSISTING OF AN ALALKYL AMINE HAVING FROMBOUT 2 TO ABOUT 12 CARBON ATOMS, AN ALIPHATIC DIAMINE OF THE GENERALFORMULA H2N(CH2)YNH2 WHEREIN Y IS AN INTEGER OF FROM ABOUT 3 TO ABOUT10, AND A POLYALKYLENE POLYAMINE OF THE GENERAL FORMULA
 2. Theoil-soluble condensation product of claim 1, wherein said copolymercomprises essentially ethylene and from about 30 to about 65 molepercent propylene.
 3. The oil-soluble condensation product of claim 1,wherein said copolymer comprises essentially ethylene, from about 30 toabout 65 mole percent propylene, and up to about 20 mole percent of athird olefinic monomer selected from the group having the generalformula RCH CH2 wherein R is an aliphatic or cycloaliphatic radical offrom 2 to about 20 carbon atoms, and diolefinic monomers having fromabout 4 to about 25 carbon atoms.
 4. The oil-soluble condensationproduct of claim 3, in which the third olefinic monomer is 1-decene. 5.The oil-soluble condensation product of claim 1, in which theformaldehyde-yielding reactant is paraformaldehyde, and the aliphaticdiamine is hexamethylene diamine.
 6. The oil-soluble condensationproduct of claim 1, in which the formaldehyde-yielding reactant isparaformaldehyde, and the polyalkylene polyamine is tetraethylenepentamine.
 7. The oil-soluble condensation product of claim 1, in whichthe copolymer comprises essentially and about 38-42 mole percentpropylene, said copolymer having a number average molecular weight offrom about 25,000 to about 35,000, and from about 160 to about 170pendant methyl groups per 1,000 chain carbon atoms, saidformaldehyde-yielding reactant is paraformaldehyde, and said aliphaticdiamine is hexamethylene diamine, said reactants being employed in themolar ratio of about 1:14.5:14.5, respectively.
 8. A lubricantcomposition comprising a major proportion of a normally liquidoleaginous lubricant, and from about 0.1 to about 10 percent of theoil-soluble condensation product defined in claim
 1. 9. A lubricantcomposition comprising a major proportion of a normally liquidoleaginous lubricant, and from about 0.1 to about 10 percent of theoil-soluble condensation product defined in claim
 2. 10. A lubricantcomposition comprising, a major proportion of a normally liquidoleaginous lubricant, and from about 0.1 to about 10 percent of theoil-soluble condensation product defined in claim
 3. 11. A lubricantcomposition comprising, a major proportion of a normally liquidoleaginous lubricant, and from about 0.1 to about 10 percent of theoil-soluble condensation defined in claim
 4. 12. A lubricant compositioncomprising, a major proportion of a normally liquid oleaginouslubricant, and from about 0.1 to about 10 percent of the oil-solublecondensation product defined in claim
 6. 13. An addition agentconcentrate for lubricating oils, comprising a lubricating oilcontaining from about 10 to about 75 percent of the oil-solublecondensation product defined in claim